The advantages of biodiesel as an alternative fuel and the problems involved in its manufacturing are outlined. The pros and cons of making biodiesel via fatty acid esterification using solid acid catalysts are examined. The main problem is finding a suitable catalyst that is active, selective, and stable under the process conditions. Various solid acids (zeolites, ion-exchange resins, and mixed metal oxides) are screened as catalysts in the esterification of dodecanoic acid with 2-ethylhexanol, 1-propanol, and methanol at 130 -180 8C. The most promising candidate is found to be sulphated zirconia. The catalysts stability towards thermal decomposition and leaching is tested and the effects of the surface composition and structure on the catalytic activity are discussed.

The concept of an organic reaction between two macroscopic solid particles is investigated. Thus, we study several reactions that have been recently reported to proceed "in the solid phase" and clearly show that, in most cases, grinding the two solid reactants together results in the formation of a liquid phase. This is true both for catalytic transformations (e.g., aldol condensations and oligomerization of benzylic compounds) and for noncatalytic reactions (Baeyer-Villiger oxidations, oxidative coupling of naphthols using iron chloride, condensation of amines and aldehydes to form azomethines, homo-etherification of benzylic alcohols using p-toluenesulfonic acid, and nuclear aromatic bromination with NBS). This liquefaction implies the existence of a eutectic mixture with T(fusion) below ambient temperature (although both reagents have higher than ambient melting points). In cases where heating is required, it is again clear that a phase change (from solid to liquid) occurs, explaining the observed reaction kinetics. On the basis of 19 experimental examples, we discuss the possibility of solid-phase organic reactions and the implications of these findings to the reaction between two solid reagents. A general description of such reactive systems is proposed, based on a consideration of the potential for eutectic (or peritectic) formation between the constituents of the liquid phases that arise during the process of mechanical mixing of the solid reagents and products.

Wood to chemicals is the subject of this short critical review, that outlines the chemical and economic aspects of several short-term and long-term perspectives for the valorisation of lignin to aromatics, polymers and materials.

This perspective examines the state-of-the-art of catalysis by metal nanoparticles. We outline various methods for preparing metal nanoparticle suspensions, and highlight the role of the stabilizers and the stabilizing principles. Subsequently, we examine some catalytic applications of homometallic and bimetallic nanoparticle suspensions in a variety of reactions. The cases are divided according to the stabilizing agent: polymers, dendrimers, ionic liquids, surfactants, micelles and micoremulsions, ligands and solid supports. We explain the importance of atom/ion leaching (all too frequent in nanoparticle catalysis, especially for the catalytically active group VIII metals) and consider ways of minimizing it. The future perspectives of nanoparticles as catalysts are discussed.

Extraction of dibenzothiophene from dodecane using ionic liquids as the extracting phase has been investigated for a range of ionic liquids with varying cation classes (imidazolium, pyridinium, and pyrrolidinium) and a range of anion types using liquid-liquid partition studies and QSPR (quantitative structure-activity relationship) analysis. The partition ratio of dibenzothiophene to the ionic liquids showed a clear variation with cation class (dimethylpyridinium . methylpyridinium . pyridinium # imidazolium # pyrrolidinium), with much less significant variation with anion type. Polyaromatic quinolinium-based ionic liquids showed even greater extraction potential, but were compromised by higher melting points. For example, 1-butyl-6-methylquinolinium bis{(trifluoromethyl)sulfonyl}amide (mp 47 uC) extracted 90% of the available dibenzothiophene from dodecane at 60 uC.

Go bio! We assess the biobased productions of three important bulk chemicals: acrylic acid, adipic acid and ε-caprolactam. These are the key monomers for high-end polymers and are all produced globally in excess of two million metric tons per year.

Leaching of palladium species from Pd nanoparticles under C--C coupling conditions was observed for both Heck and Suzuki reactions by using a special membrane reactor. The membrane allows the passage of palladium atoms and ions, but not of species larger than 5 nm. Three possible mechanistic scenarios for palladium leaching were investigated with the aim of identifying the true catalytic species. Firstly, we examined whether or not palladium(0) atoms could leach from clusters under non-oxidising conditions. By using our membrane reactor, we proved that this indeed happens. We then investigated whether or not small palladium(0) clusters could in fact be the active catalytic species by analysing the reaction composition and the palladium species that diffused through the membrane. Neither TEM nor ICP analysis supported this scenario. Finally, we tested whether or not palladium(II) ions could be leached in the presence of PhI by oxidative addition and the formation of [Pd(II)ArI] complexes. Using mass spectrometry, UV-visible spectroscopy and 13C NMR spectroscopy, we observed and monitored the formation and diffusion of these complexes, which showed that the first and the third mechanistic scenarios were both possible, and were likely to occur simultaneously. Based on these findings, we maintain that palladium nanoparticles are not the true catalysts in C--C coupling reactions. Instead, catalysis is carried out by either palladium(0) atoms or palladium(II) ions that leach into solution.

A small library of copper and noble metal nanoclusters is designed and synthesized. These clusters are tested as catalysts in the Suzuki cross-coupling of various aryl halides with phenylboronic acid. It is found that copper and copper/noble metal combination nanoclusters are active catalysts for this reaction, the most active being the combined copper/palladium clusters. Iodo-, bromo-, and chloroarenes can be used. In the case of p-nitrobromobenzene, a one-pot cross-coupling and selective hydrogenation is achieved.